US2009346A - Amido sulfonic acids and process for their preparation - Google Patents
Amido sulfonic acids and process for their preparation Download PDFInfo
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- US2009346A US2009346A US657261A US65726133A US2009346A US 2009346 A US2009346 A US 2009346A US 657261 A US657261 A US 657261A US 65726133 A US65726133 A US 65726133A US 2009346 A US2009346 A US 2009346A
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- sulfonic acids
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- -1 Amido sulfonic acids Chemical class 0.000 title description 23
- 238000000034 method Methods 0.000 title description 17
- 238000002360 preparation method Methods 0.000 title description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 24
- 150000002430 hydrocarbons Chemical group 0.000 description 19
- 150000001412 amines Chemical class 0.000 description 18
- 150000001408 amides Chemical class 0.000 description 13
- 125000005843 halogen group Chemical group 0.000 description 13
- 150000001447 alkali salts Chemical class 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000002723 alicyclic group Chemical group 0.000 description 8
- 150000003460 sulfonic acids Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229950005499 carbon tetrachloride Drugs 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005608 naphthenic acid group Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
- C07C309/18—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton containing amino groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/22—Amides or hydrazides
- C09K23/24—Amides of higher fatty acids with aminoalkylated sulfonic acids
Definitions
- wetting-out, dispersing-, latheringand cleansing-agents are attained by converting unsubstituted or monosubstituted amines, whereby at least one of the 5 radicals adhering to the nitrogen is a higher molecular hydrocarbon-residue of the aliphatic or alicyclic series, with halogenated carboxylic acids possessing one or several movable halogen atoms, or with their anhydrides or chlorides, into 10 the corresponding halogenated acidamides and. thereupon by substituting sulfonic groups for one or several of the halogen atoms.
- the present procedure is based upon the following reaction
- the producing of the amines employed is done by well-known methods as for example by a disintegration of the corresponding high molecular fatty acids or naphthenic acids by means of hydrazoic acid, or by the converting of hydro-halogenic esters of high molecular alcohols with ammonia or primary amines, whereby the latter may be substituted by hydroxylic hydrocarbon residues.
- R means a high molecular hydrocarbonresidue of the aliphatic or alicyclicseries
- R. means. hydrogen or any high or low molecular hy- 35 drocarbon-residue, which may moreover contain hydroxyl-groups.
- R means a polyvalent, high or low molecular hydrocarbon-residue, which may likewise be hydroxyl substituted, provided that the halogenated carboxylic acid serving as initial 40 product is an hydroxy-acid. represents the number of the sulfonic-groups depending upon the number of the movable halogen atoms which as a rule is 1 or 2.
- the converting of the corresponding amine with the halogenated carboxylic acid is done by'heating, and the use of a moderate vacuum will be useful for the purpose. If instead of the free carboxylic acid one employs its anhydride or chloride, the converting can be performed also under normal temperature and'by the use of a neutral dissolving or diluting agent, such as ether, benzol, carbon-tetrachloride and the like.
- a neutral dissolving or diluting agent such as ether, benzol, carbon-tetrachloride and the like.
- the substituting of the sulfonic groups for the halogen atom or halogen atoms respectively is done in the simplest manner by converting with alkali-sulphites under boiling in a reflux condenser or by pressure in the autoclave.
- the primarily resulting halogenated carboxylic acidamides may also be treated with disulphides and the thus obtained sulphur compound can be converted into the corresponding sulpho-acid by subsequent oxidation.
- This oxidation may be brought about by means of strong oxidation agents such as nitric acid, permanganate of potassium, hydrogen peroxide, hypochlorites or the like, to which small quantities of oxidation catalysts such for instance as ammonium metavanadinate may be added for increasing the oxidizing action.
- the carboboxylic-amide-monoor polysul phonic acids obtained by this procedure and monoor disubstituted on the nitrogen atom represent capillary active substances which in the form of'their alkalior ammonium salts are of an extraordinary strength, and, in contradistinction to the amines they are based on, they are not poisonous. In acidic, neutral and alkaline solutions they are stable. Used with limeor magnesia-hard water they do not separate any substances.
- Example -1 241 parts by weight of cetylamine which for instance have been obtained by converting cetylchloride with a great excess of ammonia in the presence of butyl-alcohol as a solvent, in an autoclave at 180 C. and by fractionating the obtained mixture in vacuo, are heated, eventually under moderate vacuum, with 108,5 parts of ,3- chlor-propionic acid up to 160-230" C. and until water is all separated off. The residue is boiled under reflux with an alcoholic solution of parts of sodium disulphide until the sodium chloride is likewise separated ofi. Thereupon the alcohol is evaporated, the residue is washed out by warm water and brought into a mixture warmed to 55-60 C.
- Example 2 205 parts by weight of dodecylchloride (from lauryl alcohol) are heated for some hours with '70 parts of fl-hydroxyethylamine up to the boiling point of the latter until the mass has become solid. Then one dilutes with excess sodium lye, shakes outwith ether or benzol, takes off from the aqueous layer and dries the upper layer with solid caustic lime, then one decants and after an addition of 80 parts of pyridine to the etherous or benzolic solution respectively, 113 parts of chloracetyl-chloride are dropped in under cooling with ice. Now one stirs for some time, dilutes with cold water, takes up the upper layer, dries it and evaporates the solvent.
- dodecylchloride from lauryl alcohol
- Example 3 1 gram-molecule of naphthenyl-amine such as can be obtained by the converting of naphthenic acids of the fraction Kpm -170" C. with hydrazoic acid, is dissolved in 1000 grammes of an indifferent organic solvent (ether, benzol,- carbon tetrachloride or the like), then the solution is diluted with 125 grammes of dimethylaniline and cooled with ice.
- an indifferent organic solvent ether, benzol,- carbon tetrachloride or the like
- R represents a high molecular monovalent hydro-carbon radical of the aliphatic or alicyclic series, R hydrogen or a mono-valent hydro-carbon radical, R, a poly-valent hydrocarbon radical and x the number of the sulfonic acid groups (1 or more).
- R. represents a high molecular mono-valent aliphatic hydro-carbon radical.
- R represents a mono-valent high molecular hydro-carbon radical and wherein at least one SOsI-I group is connected at the end of the R chain.
- R represents a mono-valent low molecular hydrocarbon radical and wherein at least one SO3H group is connected at the end of the R chain.
- amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen atom is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with material of the group consisting of the halogenated carboxylic acids having one or more halogen atoms inthe radical, anhydrides and chlorides of such halogenated carboxylic acids to produce halogenated acid amides, and treating the .amides to substitute sulfonic acid groups for one or more of the halogen atoms to produce sulfonic acids.
- amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with a halogenated carboxylic acid having one or more halogen atoms in the hydro-carbon radical at a temperature of the order of 160 to 230 C. to produce halogenated acid amide and reacting the amide with an alkali sulfite to substitute sulfonic acid radicals for one or more of the halogen atoms of the hydrocarbon radicals.
- the process of producingamido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with a halogenated carboxylic acid having one or more halogen atoms in the hydro-carbon radical at an elevated temperature to produce halogenated acid amide and treating the amide to substitute sulfonic acid radicals for one or more of the halogen atoms of the hydro-carbon radicals.
- amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with a halogenated carboxylic acid having one or more halogen atoms in the hydro-carbon radical at an elevated temperature and at sub-atmospheric pressure to produce halogenated acid amide and treating the amide to substitute sulfonic acid groups for one or more of the halogen atoms of the hydro-carbon radicals to produce sulfonic acids.
- amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consist- 18.
- amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with anhydrides of halogenated carboxylic acid in the presence of a diluent of the group consisting of ether, benzol and carbon-tetra-chloride and treating the product to. substitute sulfonic acid radicals for the halogen radical to. produce sulfonic acid.
- step 20 In the process of producing amido sulfonic acids the step which consists of converting halogenated carboxylic acid amides into sulfonic acids by treating the same with disulfides to produce sulfur compounds and oxidizing the sulfur compound to sulfonic acids by subjecting to the action of oxidizing agents of the group consisting of nitric acid, permanganate of potassium, hydrogen peroxide and hypochlorides.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented July 23, 1935 UNITED STATES PATENT OFFICE AMIDO SULFONIC ACIDS AND PROCESS FOR THEIR PREPARATION No Drawing.
Application February 17, 1933,
Serial No. 657,261. In Germany February 17,
23 Claims.
It has been found that excellent wetting-out, dispersing-, latheringand cleansing-agents are attained by converting unsubstituted or monosubstituted amines, whereby at least one of the 5 radicals adhering to the nitrogen is a higher molecular hydrocarbon-residue of the aliphatic or alicyclic series, with halogenated carboxylic acids possessing one or several movable halogen atoms, or with their anhydrides or chlorides, into 10 the corresponding halogenated acidamides and. thereupon by substituting sulfonic groups for one or several of the halogen atoms. The present procedure is based upon the following reaction The producing of the amines employed is done by well-known methods as for example by a disintegration of the corresponding high molecular fatty acids or naphthenic acids by means of hydrazoic acid, or by the converting of hydro-halogenic esters of high molecular alcohols with ammonia or primary amines, whereby the latter may be substituted by hydroxylic hydrocarbon residues. .Accordingly in the above reaction equations R means a high molecular hydrocarbonresidue of the aliphatic or alicyclicseries and R. means. hydrogen or any high or low molecular hy- 35 drocarbon-residue, which may moreover contain hydroxyl-groups. R means a polyvalent, high or low molecular hydrocarbon-residue, which may likewise be hydroxyl substituted, provided that the halogenated carboxylic acid serving as initial 40 product is an hydroxy-acid. represents the number of the sulfonic-groups depending upon the number of the movable halogen atoms which as a rule is 1 or 2.
The converting of the corresponding amine with the halogenated carboxylic acid is done by'heating, and the use of a moderate vacuum will be useful for the purpose. If instead of the free carboxylic acid one employs its anhydride or chloride, the converting can be performed also under normal temperature and'by the use of a neutral dissolving or diluting agent, such as ether, benzol, carbon-tetrachloride and the like. The substituting of the sulfonic groups for the halogen atom or halogen atoms respectively is done in the simplest manner by converting with alkali-sulphites under boiling in a reflux condenser or by pressure in the autoclave.
The primarily resulting halogenated carboxylic acidamides may also be treated with disulphides and the thus obtained sulphur compound can be converted into the corresponding sulpho-acid by subsequent oxidation. This oxidation may be brought about by means of strong oxidation agents such as nitric acid, permanganate of potassium, hydrogen peroxide, hypochlorites or the like, to which small quantities of oxidation catalysts such for instance as ammonium metavanadinate may be added for increasing the oxidizing action.
The carboboxylic-amide-monoor polysul phonic acids obtained by this procedure and monoor disubstituted on the nitrogen atom, represent capillary active substances which in the form of'their alkalior ammonium salts are of an extraordinary strength, and, in contradistinction to the amines they are based on, they are not poisonous. In acidic, neutral and alkaline solutions they are stable. Used with limeor magnesia-hard water they do not separate any substances.
Owing totheir excellent wetting-out, dispersing, latheringand cleansing capacity they are fitted for the treating of textiles, particularly for dyeing, washing, mercerizing, dressing and reviving. For this purpose they are employed in analogous manner and in similar proportions as other textile treating agents of the kind such as for example the sulphuric acid ester salts of high molecular fatty alcohols, from which they however differ advantageously by a much higher stability to lime and magnesia. Owing to their high dispersing capacity they are likewise fitted for the manufacture of emulsions of greases, oils and waxes. They are also capable of use in combination with other well-known wetting-out, dispersingand cleansing-agents.
In the following some characteristic examples are given merely in order to explain the invention and not to limit in any way the extension of the latter.
Example -1 241, parts by weight of cetylamine which for instance have been obtained by converting cetylchloride with a great excess of ammonia in the presence of butyl-alcohol as a solvent, in an autoclave at 180 C. and by fractionating the obtained mixture in vacuo, are heated, eventually under moderate vacuum, with 108,5 parts of ,3- chlor-propionic acid up to 160-230" C. and until water is all separated off. The residue is boiled under reflux with an alcoholic solution of parts of sodium disulphide until the sodium chloride is likewise separated ofi. Thereupon the alcohol is evaporated, the residue is washed out by warm water and brought into a mixture warmed to 55-60 C. and consisting of 275 parts of nitric acid (60-62%) and 600 parts of 50% acetic acid to which mixture 0,2 part of ammonium metavanadinate has been-added. Then one heats to 60 C. under stirring until the development of nitric oxide is finished, whereupon parts of sodium sulphate are added; after cooling the deposited propioncetylamide-fi-sulfonic acid sodium salt C16H33-NH-CO-CH2CH2SO3N9, iS filtered off; the latter can be gained pure by recrystallizing from water. The thus obtained product distinguishes itself by a high lathering and dispersing capacity, for instance in the manufacture of aqueous wax-emulsions. Such an emulsion is obtained for instance in dissolving 1 to 2 grammes of the present product in 1 liter of hot water, whereupon 10 parts of a natural wax are brought into the hot solution.
Example 2 205 parts by weight of dodecylchloride (from lauryl alcohol) are heated for some hours with '70 parts of fl-hydroxyethylamine up to the boiling point of the latter until the mass has become solid. Then one dilutes with excess sodium lye, shakes outwith ether or benzol, takes off from the aqueous layer and dries the upper layer with solid caustic lime, then one decants and after an addition of 80 parts of pyridine to the etherous or benzolic solution respectively, 113 parts of chloracetyl-chloride are dropped in under cooling with ice. Now one stirs for some time, dilutes with cold water, takes up the upper layer, dries it and evaporates the solvent. The residue is taken in alcohol and boiled under reflux with a concentrated aqueous solution of 350 parts of crystallized sodium sulphite until the transformation is terminated. Thereupon the alcohol is distilled off and the residue is recrystallized from water. By this one obtains the dodecylhydroxyethyl acetamide sulfonic acid sodium salt 2 grams of this product dissolved in 1 liter of water, give a wetting-out-bath which wets out cotton and wool very quickly and promotes remarkably the uniform going on of the color during the subsequent dyeing with direct dyestufi's.
Example 3 1 gram-molecule of naphthenyl-amine such as can be obtained by the converting of naphthenic acids of the fraction Kpm -170" C. with hydrazoic acid, is dissolved in 1000 grammes of an indifferent organic solvent (ether, benzol,- carbon tetrachloride or the like), then the solution is diluted with 125 grammes of dimethylaniline and cooled with ice. Under stirring 182 grammes of tri-chlor-acetyl-chloride are dropped in and the process is continued as per Example 2 but with the diiference that the layer of solvent must be shaken out by means of diluted hydrochloric acid until complete elimination of the dimethyl-aniline, and that three times the therein indicated quantity of sodium sulphite is required. The thus obtained naphthenyl-acetamide-disul- Ionic acid sodium salt imparts a soft feel to the artificial silk in using it as an addition to the dye-bath.
What I claim is:-
1. An alkali salt of a carboxylic amide sulfonic acid of the general formulaooR -(so3H).
in which R represents a high molecular monovalent hydro-carbon radical of the aliphatic or alicyclic series, R hydrogen or a mono-valent hydro-carbon radical, R, a poly-valent hydrocarbon radical and x the number of the sulfonic acid groups (1 or more).
2.-An alkali salt, as defined in claim 1, wherein R. represents a high molecular mono-valent aliphatic hydro-carbon radical.
3. An alkali salt, as defined in claim 1, wherein R represents a high molecular mono-valent alicyclic hydro-carbon radical.
4. An alkali salt, as defined in claim 1, wherein R represents a mono-valent high molecular hydro-carbon radical.
5. An alkali salt, as defined in claim 1, wherein R represents a mono-valent low molecular hydro-carbon radical.
6. An alkali salt, as defined in claim 1, wherein R represents a 'mono-valent hydroxyl substituted hydro-carbon radical.
'7. An alkali salt, as defined in claim 1, wherein R2 represents a poly-valent high molecular hydrocarbon radical.
8. An alkali salt, as defined in claim 1, wherein R represents a poly-valent high molecular hydrocarbon radical.
9. An alkali salt, as defined in claim 1, wherein R represents a poly-valent hydroxyl substituted hydro-carbon radical.
10. An alkali salt as defined in claim 1, wherein at least one SO3H group is connected at the end of the R. chainas a terminal group.
11. An alkali salt as defined in claim 1, wherein R represents a mono-valent high molecular hydro-carbon radical and wherein at least one SOsI-I group is connected at the end of the R chain.
12. An alkali salt as defined in claim 1, wherein R represents a mono-valent low molecular hydrocarbon radical and wherein at least one SO3H group is connected at the end of the R chain.
13. The process of producing amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen atom is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with material of the group consisting of the halogenated carboxylic acids having one or more halogen atoms inthe radical, anhydrides and chlorides of such halogenated carboxylic acids to produce halogenated acid amides, and treating the .amides to substitute sulfonic acid groups for one or more of the halogen atoms to produce sulfonic acids.
14. The process of producing amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with a halogenated carboxylic acid having one or more halogen atoms in the hydro-carbon radical at a temperature of the order of 160 to 230 C. to produce halogenated acid amide and reacting the amide with an alkali sulfite to substitute sulfonic acid radicals for one or more of the halogen atoms of the hydrocarbon radicals.
15. The process of producingamido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with a halogenated carboxylic acid having one or more halogen atoms in the hydro-carbon radical at an elevated temperature to produce halogenated acid amide and treating the amide to substitute sulfonic acid radicals for one or more of the halogen atoms of the hydro-carbon radicals.
16. The process of producing amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with a halogenated carboxylic acid having one or more halogen atoms in the hydro-carbon radical at an elevated temperature and at sub-atmospheric pressure to produce halogenated acid amide and treating the amide to substitute sulfonic acid groups for one or more of the halogen atoms of the hydro-carbon radicals to produce sulfonic acids.
17. The process of producing amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consist- 18. In the process of producing amido sultonic acids the step which comprises reacting amines of the group consisting or unsubstituted or monosubstituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with an'- hydrides of halogenated carboxylic acid in the presence of a neutral diluent to produce halogenated acid amides.
19. The process of producing amido sulfonic acids which comprises reacting amines of the group consisting of unsubstituted or mono-substituted amines wherein at least one radical attached to the nitrogen is of the group consisting of the higher molecular hydro-carbon radicals of the aliphatic and alicyclic series with anhydrides of halogenated carboxylic acid in the presence of a diluent of the group consisting of ether, benzol and carbon-tetra-chloride and treating the product to. substitute sulfonic acid radicals for the halogen radical to. produce sulfonic acid.
20. In the process of producing amido sulfonic acids the step which consists of converting halogenated carboxylic acid amides into sulfonic acids by treating the same with disulfides to produce sulfur compounds and oxidizing the sulfur compound to sulfonic acids by subjecting to the action of oxidizing agents of the group consisting of nitric acid, permanganate of potassium, hydrogen peroxide and hypochlorides.
21. In the process of producing amido sulfonic acids the step defined in claim 20 wherein the oxidation is performed in the presence of ammonium metavanadinate.
22. In the process of producing amido sulfonic acids the step which consists in converting halogenated carboxylic 'acid amides into sulfonic acids by reacting the same with alkali suliltes substantially at boiling temperature under pressure in an autoclave.
23. In the process of producing amido sulfonic acids the step which consists in converting halogenated carboxylic acid amides into sulfonic acids by boiling the same with alkali sulfites in a reflux condenser.
ERIK SCI-IIRM.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2967872A (en) * | 1958-12-18 | 1961-01-10 | Procter & Gamble | Process for making acyl taurides |
US3317589A (en) * | 1963-04-19 | 1967-05-02 | American Cyanamid Co | Alkali metal sulfo-n-alkylpropionamides |
US3529016A (en) * | 1966-03-23 | 1970-09-15 | Lever Brothers Ltd | N-(2-alkyl)-sulfoacetamides |
US4206045A (en) * | 1978-12-07 | 1980-06-03 | American Cyanamid Company | Process for froth flotation of phosphate using combination collector |
US5248811A (en) * | 1989-07-25 | 1993-09-28 | Fuji Photo Film Co., Ltd. | Process for producing sulfoalkyl-substituted hydroxylamines |
-
1933
- 1933-02-17 US US657261A patent/US2009346A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2967872A (en) * | 1958-12-18 | 1961-01-10 | Procter & Gamble | Process for making acyl taurides |
US3317589A (en) * | 1963-04-19 | 1967-05-02 | American Cyanamid Co | Alkali metal sulfo-n-alkylpropionamides |
US3529016A (en) * | 1966-03-23 | 1970-09-15 | Lever Brothers Ltd | N-(2-alkyl)-sulfoacetamides |
US4206045A (en) * | 1978-12-07 | 1980-06-03 | American Cyanamid Company | Process for froth flotation of phosphate using combination collector |
US5248811A (en) * | 1989-07-25 | 1993-09-28 | Fuji Photo Film Co., Ltd. | Process for producing sulfoalkyl-substituted hydroxylamines |
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